CN105591112A - Lithium air battery air electrode and preparation method - Google Patents

Lithium air battery air electrode and preparation method Download PDF

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Publication number
CN105591112A
CN105591112A CN201510974207.3A CN201510974207A CN105591112A CN 105591112 A CN105591112 A CN 105591112A CN 201510974207 A CN201510974207 A CN 201510974207A CN 105591112 A CN105591112 A CN 105591112A
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China
Prior art keywords
nano particle
electrode
mno
lithium
air electrode
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CN201510974207.3A
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Chinese (zh)
Inventor
银凤翔
李国儒
何小波
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Changzhou Institute for Advanced Materials Beijing University of Chemical Technology
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Changzhou Institute for Advanced Materials Beijing University of Chemical Technology
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Priority to CN201510974207.3A priority Critical patent/CN105591112A/en
Publication of CN105591112A publication Critical patent/CN105591112A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • H01M4/8652—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites as mixture
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
    • H01M4/8673—Electrically conductive fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Nanotechnology (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Hybrid Cells (AREA)
  • Inert Electrodes (AREA)

Abstract

The invention discloses a lithium air battery air electrode and a preparation method. The air electrode is composed of a porous NbN nanotube and active components. The active components are loaded or deposit in the porous NbN nano structure through an electro-deposition, chemical deposition or high-temperature nitriding method. Precious metal in air electrode materials can be reduced or even be eliminated, and therefore cost of a lithium air battery can be greatly reduced, and an oxygen electrode is simple in structure, easy to assemble and convenient to use.

Description

A kind of air electrode for lithium air battery and preparation method
Technical field
The invention belongs to battery technology field, be specifically related to a kind of air electrode for lithium air battery and preparation method.
Background technology
Along with skyrocketing of fossil class A fuel A price, replace petroleum-type product by efficient power supply, thereby for motor vehicles provide power support,Become an urgent demand of modern social development. Find specific energy higher, more cheap positive electrode is the developing direction of lithium battery always, but lithium electricityIn pond, positive electrode has limited to the energy storage capacity of lithium battery, such as the electrochemistry capacitance of lithium metal is 3860mAh/g, but the electricity of most of positive electrodeChemical capacity only has 200mAh/g
On the other hand, lithium-air battery has good chemical property, as a kind of brand-new metal-air battery, as anodal oxygen (skyGas) do not need to be stored in battery. Aerial oxygen can be become negative oxygen ion or be crossed negative oxygen ion and then pass through electrochemistry by catalystReaction generates metal oxide or peroxide.
But the oxygen electrode of positive electrode current is generally noble metal catalyst (as Pt), the cost of the empty battery of lithium is increased, restrict the development of its industrializationPaces. If can successfully adopt new catalyst to replace or reduce the use of noble metal, will greatly reduce the cost of lithium-air battery, to lithium air electricityGreat progradation is played in the development in pond.
Summary of the invention
The object of the present invention is to provide a kind of air electrode for lithium air battery and preparation method, this preparation method can reduce and even remove oxygen electrode fromThe content of middle noble metal and adhesive, greatly reduces the cost of lithium-air battery, to overcome prior art deficiency.
The object of the invention is to be achieved through the following technical solutions:
A kind of air electrode for lithium air battery is made up of porous NbN nanotube and active component;
Active component is: Pt nanoparticle, gold nano grain, α-MnO2Nano particle,, β-MnO2Nano particle, γ-MnO2Nano particle,One or more in MoN nano particle, MnN nano particle, ternary metal nitride; Wherein one or both content of platinum, gold are less than oxygen4.5% of electrode gross mass.
A kind of air electrode for lithium air battery, the key step of its preparation method is:
A) by Nb sheet at NH4In F, carry out anode electrochemical corrosion, wherein Nb is as anode, and Pt sheet is as negative pole;
B) product that steps A obtains is in NH3In atmosphere, 700～950 DEG C of reduction, obtain NbN nanotube;
C) by electrochemical deposition, the active material of oxygen electrode is deposited in NbN nanotube.
In above-mentioned steps, active component is: Pt nanoparticle, gold nano grain, α-MnO2Nano particle,, β-MnO2Nano particle, γ-MnO2One or more in nano particle, MoN nano particle, MnN nano particle, ternary metal nitride; Wherein platinum, gold one or bothContent is less than 4.5% of oxygen electrode gross mass.
Air electrode of the present invention provides conductive network by the nanostructured of NbN, by chemistry, electrochemical deposition load active component, is onePlant efficient air electrode for lithium air battery system. Air electrode of the present invention can not only reduce the content of noble metal, and has good catalyticEnergy.
Detailed description of the invention
EXAMPLE l
Nb sheet is cleaned up to the NH that is 0.5% at mass fraction with ethanol4In the ethylene glycol solution of F, carry out anode electrochemical corrosion, whereinNb is as anode, and Pt sheet is as negative pole. Anodic attack current potential is 60V, and etching time is 8h. The NbO obtaining2Nanotube is at 700 DEG C, NH3High temperature reduction 1h in atmosphere, obtains NbN nanotube.
By electrochemical deposition by the nanoparticle deposition of Pt in NbN nanotube, electrolyte is 0.25mMH2PtC16Be dissolved in 0.1MHCl,Carry out electro-deposition by cyclic voltammetry. Potential region is-0.6～0.1V, and sweep speed is 20mVs-1, deposit 10 circulations, obtain Pt/NbNAir electrode. This air electrode is the square pole piece of lcm × lcm, and thickness is 100um, and wherein the NbN nano-tube array of supporting Pt nano particle is thickDegree is for 22um, and the internal diameter of sleeve structure is 50～60nm, and Pt nano particle layer thickness is 10～15nm, and the pipe thickness of NbN nanotube is 8～10nm. This air electrode can be to O2Carry out efficient catalysis, and can, directly as the oxygen electrode of lithium-air battery, collect without extra interpolationFluid binding agent and conductive agent. The specific capacity of the lithium-air battery based on this air electrode reaches 1800mAhg-1. OCP can reach 3.8V. FillPotential difference between discharge platform is 0.5V.
Embodiment 2
Nb sheet is cleaned up to the NH that is 0.5% at mass fraction with ethanol4In the ethylene glycol solution of F, carry out anode electrochemical corrosion, whereinNb is as anode, and Pt sheet is as negative pole. Anodic attack current potential is 60V, and etching time is 8h. The NbO obtaining2Nano-tube array is at 950 DEG C,NH3High temperature reduction 1h in atmosphere, obtains NbN nanotube.
By electrochemical deposition by golden nanoparticle deposition in NbN nanotube, electrolyte is 0.25mMH2AuC16Be dissolved in 0.1MHCl,Carry out electro-deposition by cyclic voltammetry. Potential region is-0.6～0.1V, and sweep speed is 20mVs-1, deposit 10 circulations, obtain Au/NbNCoaxial sleeve structure. This combination electrode is the square pole piece of lcm × lcm, and thickness is 100um, wherein the NbN nanotube of load gold nano grainArray thickness is 23um, and the internal diameter of sleeve structure is 60～70nm, and gold nano grain layer thickness is 10～15nm, the pipe thickness of NbN nanotubeBe 9～10nm. The specific capacity of the lithium-air battery based on this air electrode reaches 2000mAhg-1. OCP can reach 3.8V. Between charge and discharge platformPotential difference is 0.7V.
Embodiment 3
Nb sheet is cleaned up to the NH that is 0.5% at mass fraction with ethanol4In the ethylene glycol solution of F, carry out anode electrochemical corrosion, whereinNb is as anode, and Pt sheet is as negative pole. Anodic attack current potential is 60V, and etching time is 8h. By the NbO obtaining2Nano-tube array is placed in 1mMAmmonium molybdate solution in 1h, afterwards the pole piece of taking-up is carefully rinsed with clear water, 280 DEG C dry 3h, acquisition load is had to MoO3NbO2ReceiveMitron array is placed in tube furnace, at NH3800 DEG C of high temperature reductions in atmosphere, in temperature-rise period, programming rate is 5 DEG C of min-1. Can obtainMoN/NbN air electrode. The specific capacity of the lithium-air battery based on this air electrode reaches 2100mAhg-1. OCP can reach 3.8V. Discharge and rechargePotential difference between platform is 0.6V.
Embodiment 4
Nb sheet is cleaned up to the NH that is 0.5% at mass fraction with ethanol4In the ethylene glycol solution of F, carry out anode electrochemical corrosion, whereinNb is as anode, and Pt sheet is as negative pole. Anodic attack current potential is 60V, and etching time is 8h. By the NbO obtaining2Nano-tube array is placed in 1mMManganese sulfate and the potassium sulfate mixed solution of 1mM in 1h, afterwards the pole piece of taking-up is carefully rinsed with clear water, dry 3h for 280 DEG C, will obtain and bearBe loaded with α-MnO2NbO2Nano-tube array is placed in tube furnace, at NH3700 DEG C of high temperature reductions in atmosphere, in temperature-rise period, programming rate is 5 DEG Cmin-1. Can obtain α-MnO2/ NbN air electrode. The specific capacity of the lithium-air battery based on this air electrode can reach 2000mAhg-1. Open circuitCurrent potential reaches 3.7V. Potential difference between charge and discharge platform is 0.6V.

Claims (3)

1. air electrode for lithium air battery and a preparation method, is characterized in that, air electrode is made up of porous NbN nanotube and active component;
Active component is: Pt nanoparticle, gold nano grain, α-MnO2Nano particle,, β-MnO2Nano particle, γ-MnO2Nano particle,One or more in MoN nano particle, MnN nano particle, ternary metal nitride; Wherein one or both content of platinum, gold are less than oxygen4.5% of electrode gross mass.
2. a preparation method who prepares air electrode for lithium air battery described in claim 1, key step is:
A) by Nb sheet at NH4In F, carry out anode electrochemical corrosion, wherein Nb is as anode, and Pt sheet is as negative pole;
B) product that steps A obtains is in NH3In atmosphere, 700～950 DEG C of reduction, obtain NbN nanotube;
C) by electrochemical deposition, active component is deposited in NbN nanotube.
3. according to a kind of air electrode for lithium air battery and preparation method described in claim 1 or 2, wherein, active component is: Pt nanoparticle,Gold nano grain, α-MnO2Nano particle,, β-MnO2Nano particle, γ-MnO2Nano particle, MoN nano particle, MnN nano particle,One or more in ternary metal nitride; Wherein one or both content of platinum, gold are less than 4.5% of oxygen electrode gross mass.
CN201510974207.3A 2015-12-22 2015-12-22 Lithium air battery air electrode and preparation method Pending CN105591112A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108134059A (en) * 2017-12-20 2018-06-08 成都新柯力化工科技有限公司 A kind of negative electrode active material and preparation method for low temperature lithium battery

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103151541A (en) * 2013-03-01 2013-06-12 北京化工大学常州先进材料研究院 Novel air electrode for lithium-air battery and preparation method

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103151541A (en) * 2013-03-01 2013-06-12 北京化工大学常州先进材料研究院 Novel air electrode for lithium-air battery and preparation method

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108134059A (en) * 2017-12-20 2018-06-08 成都新柯力化工科技有限公司 A kind of negative electrode active material and preparation method for low temperature lithium battery

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